CN102089458B - Aqueous metal-surface-treating agent and surface-treated metal material - Google Patents

Aqueous metal-surface-treating agent and surface-treated metal material Download PDF

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CN102089458B
CN102089458B CN200980127516XA CN200980127516A CN102089458B CN 102089458 B CN102089458 B CN 102089458B CN 200980127516X A CN200980127516X A CN 200980127516XA CN 200980127516 A CN200980127516 A CN 200980127516A CN 102089458 B CN102089458 B CN 102089458B
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polymkeric substance
treatment agent
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water
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CN102089458A (en
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铃木龙也
山口英宏
水野贤辅
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Nihon Parkerizing Co Ltd
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/173—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • C23F11/182—Sulfur, boron or silicon containing compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/19—Iron or steel

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Abstract

Disclosed is an aqueous surface-treating agent having excellent corrosion resistance, adhesion properties, stain-proof properties, film-forming properties, ultraviolet ray resistance, alkali resistance, acid resistance, processability and storage stability. Specifically disclosed is an aqueous metal-surface-treating agent comprising the following components (A) to (E): (A) a Zr compound and/or a metal oxide zol; (B) a hydrolyzable silyl compound; (C) a polymer which has polymerization units derived from (c1) a (meth)acrylic acid ester having a specific structure, (c2) a silicon-containing monomer, (c3) an a,ss-ethylenically unsaturated carboxylic acid and (c4) another (meth)acrylic acid ester, does not contain any unsaturated bond other than a bond contained in a carbonyl group in its molecule, and has a specified Tg, a specified MFT and a specified acid value; (D) a plasticizer; and (E) an emulsifying agent, wherein the ratio of the total mass (M) of a metal or metals in the component (A) to the sum total of the mass (Si1) of silicon in the component (B) and the mass (Si2) of silicon in the component (c2) [i.e., a M/(Si1+Si2) ratio] and a Si1/Si2 ratio have specified values, and wherein the component (C) is contained in an amount of 40 to 98 mass% relative to the total solid content. Also specifically disclosed is a surface-treated metal material.

Description

Water-based metal surface treatment agent and surface-treated metal material
Technical field
The present invention relates to form the water-based metal surface treatment agent that has excellent storage stability of the overlay film of erosion resistance, adaptation, didirtresistance, film-forming properties, ultraviolet resistance, alkali resistance, acid resistance and excellent processability.
Background technology
Zinc-based metal plated steel sheet is considered from the viewpoint of excellent corrosion resistance, is widely used in building materials, household electrical appliances, car applications etc.In the purposes of building materials or household electrical appliances; Because a part of zinc-based metal plated steel sheet uses with the form of no application; Therefore; Not only require superior corrosion resistance, and the aesthetic appearances that demonstrates the plating tone can not kept because of absorption of uviolizing, acid rain, pollution substance etc. suffers erosion in the surface that requires plated steel sheet.In addition, under the situation of the face of enforcement application, require to have sufficient adaptation with face application layer.When insufficient, can't bring into play erosion resistance, acid resistance, alkali resistance with the adaptation of face application layer.In addition, steel plate is used for to carry out bending machining or extrude processing under the situation of building materials or household electrical appliances etc., therefore, requires the adaptation of overlay film and base material and the flexibility of overlay film.
In the past; As the technology of metal material surface being given erosion resistance or processibility etc.; Usually adopt to utilize and contain organic resin and chromic acid, dichromic acid or their salt and metal material surface is carried out the method for resin chromate treating, begun to use with the environment-friendly chromium-free hydrochlorate organic resin overlay film processing of other bridging property metal replacement chromium at present etc. as the treatment solution of staple.
As chromate-free organic resin overlay film treatment technology; In patent documentation 1; Disclose a kind of method of manufacture of high-weatherability emulsion, it is characterized in that, the monomer composition that will contain (methyl) propenoate, dialkyl group (methyl) acrylic amide and tensio-active agent at least carries out letex polymerization.But; High-weatherability emulsion by the aforesaid method manufacturing forms overlay film on steel plate; Do not have sufficient erosion resistance when in no application purposes, using; Moreover, also can not get sufficient adaptation, therefore can not satisfy acid resistance, the desired performance of alkali resistance even on this overlay film, carry out the face application.
In addition; As chromate-free organic resin overlay film treatment technology; In patent documentation 2; Disclose a kind of method of manufacture of corpuscle emulsion, it is characterized in that, will contain (methyl) propenoate at least, carry out letex polymerization with respect to this (methyl) propenoate vinylbenzene that is 0.1～20 quality % and the monomer composition of tensio-active agent.But, owing to contain vinylbenzene in the corpuscle emulsion by the aforesaid method manufacturing, so therefore overlay film is not suitable for outdoor no application purposes through uviolizing meeting deterioration, variable color.
In addition; As chromate-free organic resin film coating technique, in patent documentation 3, a kind of metal conditioner is disclosed; It contains water-soluble zirconium compound, water-soluble or water dispersible vinyl resin and water-soluble or water dispersible thermosetting type linking agent; It is characterized in that the zirconium in the said water-soluble zirconium compound is counted 500～15000ppm with quality criteria, the solids component acid number of said vinyl resin is that 150～740mgKOH/g, solids component hydroxyl value are 24～240; In the quality criteria solids component is 500～30000ppm, and the solids component of said heat curing-type linking agent is counted 125～7500ppm with quality criteria.But, because the heat curing-type linking agent can make overlay film solidify thereby poor in processability.In addition, melamine resin or the resol enumerated as the heat curing-type linking agent are because overlay film through uviolizing meeting deterioration, variable color, therefore is not suitable for not having the application purposes.
In addition; As chromate-free organic resin film coating technique; In patent documentation 4; Disclose a kind of sheet metal that does not contain chromium and used surface treatment agent, it is characterized in that, contained: (A) had the water-base resin of carboxyl and amido linkage, one or more metallic compound and (C) silicon compound in the metallic compound that (B) is selected from Al, Mg, Ca, Zn, Ni, Co, Fe, Zr, Ti, V, W, Mn and Ce.But, owing to the reactivity of water-base resin metallizing thing with amido linkage or silicon compound is strong, so poor storage stability.
In addition; As chromate-free organic resin film coating technique; In patent documentation 5; Disclose a kind of metallic surface and used the water-dispersed resin treatment agent; It comprises: (A) water-dispersed resin compsn; The copolymer resin fat liquor that contains the letex polymerization of unsaturated monomer mixture and obtain, said unsaturated monomer mixture by the polymerizability unsaturated monomer (styrene monomer etc.) that does not contain any group in epoxy group(ing), acidic group, hydroxyl and the water-disintegrable silyl (a), the polymerizability unsaturated monomer (e) that has the polymerizability unsaturated monomer (d) of the polymerizability unsaturated monomer (b) of epoxy group(ing), the polymerizability unsaturated monomer (c) that contains acidic group, hydroxyl and have a water-disintegrable silyl constitutes; (B) zirconium compounds; (C) silane coupling agent.But; Because the polymerizability unsaturated monomer that contains styrene monomer and have epoxy group(ing) in the overlay film that forms with the water-dispersed resin treatment agent by above-mentioned metallic surface; Therefore overlay film is through uviolizing meeting deterioration, variable color, and didirtresistance is also poor, therefore is not suitable for outdoor no application purposes.In addition, owing to the polymerizability unsaturated monomer (b) with epoxy group(ing) is strong with the reactivity of the polymerizability unsaturated monomer (c) that contains acidic group, so poor storage stability.
In addition; As chromate-free organic resin film coating technique; In patent documentation 6; A kind of water-borne coatings is disclosed; It contains resinous principle (A) and is the organic acid catalyst (C) of 0.01～10 mass parts with respect to solids component 100 mass parts of resinous principle (A), and said resinous principle (A) obtains through the monomer mixture generation Raolical polymerizable with respect to other the free-radical polymerised unsaturated monomer (c) that contains carboxyl free radical polymerizability unsaturated monomer (b) and 50～98.9 quality % that constitutes specific nitrogenous free-radical polymerised unsaturated monomer (a) that monomeric total amount contains 0.1～30 quality %, 1～20 quality %.But, insufficient by the overlay film erosion resistance that above-mentioned water-borne coatings forms, can not satisfy desired performance.
Patent documentation 1: TOHKEMY 2000-327704 communique
Patent documentation 2: TOHKEMY 2000-327722 communique
Patent documentation 3: TOHKEMY 2002-275648 communique
Patent documentation 4: TOHKEMY 2003-201579 communique
Patent documentation 5: TOHKEMY 2006-52348 communique
Patent documentation 6: TOHKEMY 2006-152056 communique
Summary of the invention
Like this; Above-mentioned any method and surface treatment agent are not talkative to have the performance that can use as the surrogate of resin chromic salt overlay film and the overlay film that can form erosion resistance, adaptation, didirtresistance, film-forming properties, ultraviolet resistance, alkali resistance, acid resistance and excellent processability, thereby the surface treatment agent and the treatment process of these performances can be comprehensively satisfied in urgent hope exploitation.
The objective of the invention is to solve the problems referred to above that prior art exists, aqueous surface-treating agent overlay film, that have excellent storage stability that can form erosion resistance, adaptation, didirtresistance, film-forming properties, ultraviolet resistance, alkali resistance, acid resistance and excellent processability is provided.
The inventor furthers investigate for addressing these problems repeatedly, and the result finds, contains: zirconium compounds and/or metal oxide sol; Water-disintegrable silyl compound; Having (methyl) acrylic ester unit, silicon-containing monomer unit, the α of ad hoc structure, β-ethylenically unsaturated carboxylic acids unit and (methyl) alkyl acrylate and/or (methyl) hydroxyalkyl acrylate unit are as not containing the unsaturated link(age) beyond the carbonyl in polymerized unit and the molecule and having the polymkeric substance of specific second-order transition temperature, minimum film-forming temperature and acid number; Softening agent; Water-based metal surface treatment agent with emulsifying agent has excellent storage stability, and can form the overlay film of erosion resistance, didirtresistance, film-forming properties, ultraviolet resistance, alkali resistance, acid resistance and excellent processability, thereby has accomplished the present invention.
The present invention relates to a kind of water-based metal surface treatment agent; Contain composition (A), water-disintegrable silyl compound (B), polymkeric substance (C), softening agent (D) and emulsifying agent (E); Said composition (A) is for being selected from least a in the group of being made up of zirconium compounds (A1) and metal oxide sol (A2); Said polymkeric substance (C) has from the polymerized unit of (methyl) propenoate (c1) of formula (I) expression, from the polymerized unit of the silicon-containing monomer (c2) of formula (III) expression, from α; The polymerized unit of β-ethylenically unsaturated carboxylic acids (c3) and from the polymerized unit of other (methyl) propenoate (c4) as polymerized unit, and do not contain the unsaturated link(age) beyond the carbonyl in the molecule, the second-order transition temperature of this polymkeric substance (C) be 0～70 ℃, minimum film-forming temperature for-5～40 ℃, acid number be 5～40mgKOH/g; Wherein
Emulsifying agent (E) is for being selected from least a in the group of being made up of reactive emulsifier (E1) and non-reacted emulsifying agent (E2); In at least a portion is under the situation of reactive emulsifier; This reactive emulsifier with the form of polymerized unit therefrom as a kind of of the polymerized unit of polymkeric substance (C) and exist; Polymkeric substance (C) is disperseed by emulsifying agent (E); The quality ratio of the total quality of the quality Si2 of the silicon that the quality Si1 of the silicon that the total mass M of the metal that composition (A) is contained and water-disintegrable silyl compound (B) are contained and silicon-containing monomer (c2) are contained [M/ (Si1+Si2)] is 0.1～50; And Si1/Si2 is 0.15～250, and the ratio of polymkeric substance (C) is 40～98 quality % with respect to all solids composition of this water-based metal surface treatment agent
Figure BPA00001294055900051
In the formula (I), R1 representes Wasserstoffatoms or methyl, and R2 representes the group shown in the general formula (II),
Figure BPA00001294055900052
In the formula (II), R3, R4 and R5 represent the alkyl of Wasserstoffatoms, hydroxyl or carbonatoms 1～3 independently of each other,
Figure BPA00001294055900053
In the formula (III), R6, R7 and R8 represent the alkyl of Wasserstoffatoms, hydroxyl, carbonatoms 1～3 or the alkoxyl group of carbonatoms 1～3 independently of each other, the group shown in X expression (IV) or the logical formula V,
Figure BPA00001294055900054
Figure BPA00001294055900061
In the formula V, R9 representes Wasserstoffatoms or methyl, and R10 representes the alkylidene group of carbonatoms 1～12.
Softening agent (D) is preferably and is selected from by 2; 2; 4-trimethylammonium-1; At least a in the group that 3-pentanediol mono isobutyrate, Diethylene Glycol single-butyl ether acetic ester, ethylene glycol monobutyl ether and dipropylene glycol n-butyl ether are formed, metal oxide sol (A2) are preferably and are selected from least a in the group of being made up of cerium oxide sol, yttrium oxide colloidal sol, Neodymium trioxide colloidal sol and lanthanum trioxide colloidal sol.
In addition, be preferably 0.1～50 mass parts from the unitary ratio of (methyl) propenoate (c1) with respect to 100 mass parts polymkeric substance (C), the ratio of emulsifying agent (E) is preferably 0.5～5 mass parts with respect to 100 mass parts polymkeric substance (C).
The invention still further relates to a kind of metallic substance, its surface has 0.05～5g/m 2The dry overlay film that forms by above-mentioned water-based metal surface treatment agent.
The invention effect
Water-based metal surface treatment agent of the present invention has excellent storage stability and can form the overlay film of erosion resistance, adaptation, didirtresistance, film-forming properties, ultraviolet resistance, alkali resistance, acid resistance and excellent processability.Therefore, the overlay film measurer with regulation has the metallic substance of the dry overlay film that is formed by above-mentioned water-based metal surface treatment agent, erosion resistance, adaptation, didirtresistance, film-forming properties, ultraviolet resistance, alkali resistance, acid resistance and excellent processability on the surface.
Embodiment
The water-based metal surface treatment agent that has excellent storage stability of the present invention contains at least a, water-disintegrable silyl compound (B), polymkeric substance (C), softening agent (D) and the emulsifying agent (E) in the group of being made up of zirconium compounds (A1) and metal oxide sol (A2) that be selected from as composition (A).
Composition (A) as the neccessary composition of treatment agent of the present invention is zirconium compounds (A1) and/or metal oxide sol (A2).
Zirconium compounds (A1)
Zirconium compounds (A1) is layered laminate in overlay film, can suppress the oxygen-permeable and the water vapor transmission of formed overlay film, brings into play very good barriering effect, and erosion resistance is improved.In addition, zirconium is high to the weather resistance of alkalescence, so zirconium compounds (A1) can improve alkali resistance.
As zirconium compounds (A1), can enumerate: fluorine zirconic acid, ammonium fluozirconate, zirconium nitrate, acetic acid zirconium, zirconium white, zirconium nitrate, zirconium carbonate ammonium, potassium zirconium carbonate, alkaline carbonic acid zirconium, zirconium stearate, zirconium caprylate, methyl ethyl diketone zirconium, three butoxy single acetyl acetone zirconiums, methyl ethyl diketone zirconium, zirconium-n-propylate, zirconium-n-butylate, three butoxy Stearinsaeure zirconiums etc.
Metal oxide sol (A2)
Metal oxide sol (A2) is layered laminate in overlay film, can suppress the oxygen-permeable and the water vapor transmission of formed overlay film, brings into play very good barriering effect, and erosion resistance is improved.Particularly rare earth oxide has the isolated effect of ultraviolet ray, the uv degradation of the polymkeric substance (C) that therefore can further suppress to be caused by uviolizing.
As metal oxide sol (A2), can enumerate: Natural manganese dioxide colloidal sol, alumina sol, silica sol, quicklime colloidal sol, Scium trioxide colloidal sol, titanium oxide sol, vanadium oxide colloidal sol, manganese oxide colloidal sol, gallium oxide colloidal sol, germanium oxide colloidal sol, yttrium oxide colloidal sol, acidifying zirconium colloidal sol, antimony oxide sol, lanthanum trioxide colloidal sol, cerium oxide sol, Neodymium trioxide colloidal sol, hafnia colloidal sol etc.Wherein, isolated good especially cerium oxide sol, yttrium oxide colloidal sol and the Neodymium trioxide colloidal sol of effect of preferred especially ultraviolet ray.
Water-disintegrable silyl compound (B)
Water-disintegrable silyl compound (B) improves the adaptation of formed overlay film and base material or overlay film and face application layer, therefore can improve erosion resistance, erosion resistance and alkali resistance.Among the present invention, water-disintegrable silyl compound (B) is meant the compound of formula (VI) expression.
Figure BPA00001294055900081
(in the formula; R11 representes the alkoxyl group of carbonatomss 1～3 such as alkyl or methoxyl group, oxyethyl group, the isopropoxy of carbonatomss such as Wasserstoffatoms, hydroxyl, methyl, ethyl, sec.-propyl 1～3; R12 and R13 represent the alkyl of carbonatomss 1～3 such as Wasserstoffatoms, methyl, ethyl, sec.-propyl independently of each other, and Y representes chain or cyclic alkyl or the vinyl by hydroxyl, amino, N-aminoethylamino, glycidyl oxygen base or the substituted carbonatoms 1～6 of sulfydryl).
As water-disintegrable silyl compound (B); Specifically can enumerate: N-(amino-ethyl)-3-TSL 8330,3-aminopropyltriethoxywerene werene, 3-glycidoxy-propyltrimethoxy silane, 3-epoxypropoxy methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, vinyltriethoxysilane, 3-sulfydryl propyl trimethoxy silicane, 3-methyl allyl acyloxypropyl trimethoxysilane etc.
Polymkeric substance (C)
Polymkeric substance (C) is with from the polymerized unit of (methyl) propenoate (c1) with ad hoc structure, from the polymerized unit of the silicon-containing monomer with ad hoc structure (c2), from α; The polymerized unit of β-ethylenically unsaturated carboxylic acids (c3), from the polymerized unit of other (methyl) propenoate (c4) and when having reactive emulsifier (E1) from the polymerized unit of this reactive emulsifier (E1) as polymerized unit; And do not contain the unsaturated link(age) beyond the carbonyl in the molecule, this polymkeric substance (C) has the polymkeric substance of specific second-order transition temperature, minimum film-forming temperature and acid number.In addition, above-mentioned " from ... polymerized unit " represent that carbon-to-carbon double bond contained in each molecule is opened and the polymerized unit that forms.
In addition, when using reactive emulsifier (E1), also become the polymerized unit that constitutes polymkeric substance (C) from the polymerized unit of reactive emulsifier (E1) as at least a portion of the emulsifying agent that uses in the treatment agent of the present invention (E).About reactive emulsifier (E1), describe in the part that emulsifying agent (E) is described.
(methyl) propenoate (c1)
(methyl) propenoate (c1) is (methyl) propenoate of above-mentioned general formula (I) expression.(methyl) propenoate (c1) has the effect of the second-order transition temperature rising that makes polymkeric substance (C); Therefore can improve weather resistance and the erosion resistance of formed overlay film to temperature variation; In addition, can also improve adaptation, didirtresistance, film-forming properties, ultraviolet resistance, alkali resistance, acid resistance and processibility.
R2 in the general formula (I) must only be formed by saturated bond.When having unsaturated link(age), thereby form chromophoric group or auxochromous group, so ultraviolet resistance descends because of free radical reaction takes place in ultraviolet ray.As the alkyl of the carbonatoms 1～3 in the definition of R3, R4 and R5 in the general formula (II), can enumerate methyl, ethyl, propyl group and sec.-propyl.
As (methyl) propenoate (c1), can enumerate: vinylformic acid norbornene ester, IBOA, methylacrylic acid norbornene ester, isobornyl methacrylate etc.
Body (c2) in siliceous
Silicon-containing monomer (c2) is the silicon-containing monomer of above-mentioned general formula (III) expression.The adaptation that silicon-containing monomer (c2) enhancing overlay film and base material or overlay film and facing are filmed improves erosion resistance, alkali resistance and the acid resistance of formed overlay film.
In the definition of R6, R7 and R8 in the general formula (III),, methyl, ethyl, propyl group and sec.-propyl can be enumerated,, methoxyl group, oxyethyl group, propoxy-and isopropoxy can be enumerated as the alkoxyl group of carbonatoms 1～3 as the alkyl of carbonatoms 1～3.In the definition of R10 in the logical formula V, as the alkylidene group of carbonatoms 1～12, can enumerate: methylene radical, ethylidene, propylene, 1; 3-propylidene, tetramethylene, pentamethylene, hexamethylene, 1; The inferior heptyl of 7-, octamethylene, 2-ethyl hexane-1,6-two bases, nonamethylene, 1; The inferior decyl, 1 of 10-, the inferior undecyl, 1 of 11-, the inferior dodecyl of 12-etc.
As silicon-containing monomer (c2), specifically can enumerate: vinyltrimethoxy silane, vinyltriethoxysilane, 3-acryloyl-oxy propyl trimethoxy silicane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methyl allyl acyloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxyl silane etc.
α, β-ethylenically unsaturated carboxylic acids (c3)
α, β-ethylenically unsaturated carboxylic acids (c3) strengthens the adaptation of overlay film and base material or overlay film and face application layer, and the erosion resistance of formed overlay film is improved.
As α, β-ethylenically unsaturated carboxylic acids (c3) can be enumerated: vinylformic acid, methylacrylic acid, toxilic acid, methylene-succinic acid, fumaric acid, Ba Dousuan etc.
Other (methyl) propenoate (c4)
Polymkeric substance (C) comprises from the polymerized unit of (methyl) propenoate (c1), from the polymerized unit of silicon-containing monomer (c2), from α; The polymerized unit of β-ethylenically unsaturated carboxylic acids (c3), also comprise when having reactive emulsifier (E1) from the polymerized unit of this reactive emulsifier (E1) as constituting polymerized unit; As constituting polymerized unit, also comprise other (methyl) propenoate (c4) except that these remaining polymerized unit.Said (methyl) propenoate (c4) does not contain aromatic nucleus, epoxy group(ing) and amido linkage, different with silicon-containing monomer (c2) with (methyl) propenoate (c1) (methyl) propenoate.
As above-mentioned (methyl) propenoate (c4), can enumerate: be selected from least a (methyl) propenoate in the group of forming by (methyl) alkyl acrylate, (methyl) hydroxyalkyl acrylate and (methyl) vinylformic acid cycloalkanes ester.The carbonatoms of the alkyl of (methyl) alkyl acrylate is preferably 1～10; More preferably 1～8, the carbonatoms of the hydroxyalkyl of (methyl) hydroxyalkyl acrylate is preferably 2～10, and more preferably 2～6; Further preferred 2～4, the carbonatoms of the naphthenic base of (methyl) vinylformic acid cycloalkanes ester is preferably 5 or 6.
Particularly; Alkyl as carbonatoms 1～10; Can enumerate: methyl, ethyl, propyl group, sec.-propyl, butyl, amyl group, hexyl, heptyl, octyl group, 2-ethylhexyl, decyl etc.; As the hydroxyalkyl of carbonatoms 2～10, can enumerate: hydroxyethyl, hydroxypropyl, hydroxyl butyl, hydroxyl hexyl, hydroxyl octyl group, hydroxy decyl etc.Carbonatoms 5 or 6 naphthenic base comprise cyclopentyl and cyclohexyl.
As (methyl) propenoate (c4), specifically can enumerate: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) Bing Xisuandingzhi, (methyl) NSC 20949, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) NSC 11786, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) decyl acrylate, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) cyclohexyl acrylate etc.
Below, the rerum natura that should possess polymkeric substance (C) describes.
The second-order transition temperature of polymkeric substance (C) need be 0～70 ℃, preferred 10～60 ℃, and more preferably 20～50 ℃.Thus, to the weather resistance raising of temperature variation, can bring into play superior corrosion resistance and processibility.When second-order transition temperature is lower than 0 ℃, not only can not obtain adding required overlay film hardness in man-hour, and erosion resistance also has the tendency of decline, when surpassing 70 ℃, the overlay film tracing ability that adds man-hour descends, and the tendency that adaptation is bad, overlay film cracks is arranged.
In addition, the glass transition temperature Tg of polymkeric substance among the present invention (C) can be by each monomeric glass transition temperature Tg i (i=1,2 of using in this polymerization;, i) with weight fraction Xi (i=1,2;, i), through type 1/Tg=∑ (Xi/Tgi) calculates good approximation.
The minimum film-forming temperature of polymkeric substance (C) need be-5～40 ℃, preferred 0～30 ℃, and more preferably 5～20 ℃.When minimum film-forming temperature is lower than-5 ℃, the tendency of the stability in storage that can not get water-based metal surface treatment agent of the present invention is arranged, when surpassing 40 ℃, film-forming properties is insufficient, the tendency that has erosion resistance, alkali resistance and acid resistance to descend.
In addition, the minimum film-forming temperature of polymkeric substance (C) is confirmed according to the monomeric composition that forms polymkeric substance (C), under the situation of plastic binder (D), can change minimum film-forming temperature through its combined amount.That is,, can reduce minimum film-forming temperature through increasing the combined amount of softening agent (D).
The minimum film-forming temperature of polymkeric substance (C) can be measured through known method.Among the present invention, the thick polymkeric substance as sample of coating 0.2mm on the stainless steel plate of thermograde testing apparatus after sealing, the drying, reads the same continuous overlay film part and the temperature of the portion boundary portion that produces gonorrhoea, as minimum film-forming temperature.
The acid number of polymkeric substance (C) need be 5～40mgKOH/g, is preferably 10～30mgKOH/g, more preferably 10～25mgKOH/g.When acid number was lower than 5mgKOH/g, not only adaptation descended, and the tendency of stability in storage variation is arranged, when surpassing 40mgKOH/g, and the water-soluble enhancing of the overlay film of formation, the tendency that has alkali resistance and acid resistance to descend.
The molecular weight of polymkeric substance (C) is preferably 10000～200000 in weight-average molecular weight, and more preferably 50000～150000.This molecular weight can obtain sufficient stability in storage and film-forming properties in above-mentioned scope the time.
Softening agent (D)
Softening agent (D) has the effect of the film-forming properties that improves overlay film.Film forming promptly forms film, and the good softening agent (D) that is meant of film-forming properties gets into the gap of polymkeric substance (C), and the crystallinity of polymkeric substance (C) is descended, and promotes the fusion between particle when overlay film is dry, thereby forms concavo-convex few uniform overlay film.Consequently, the diffuse-reflectance of incident light is suppressed and the transparency raising of overlay film, and the overlay film outward appearance is improved, and erosion resistance, alkali resistance and acid resistance improve.
As softening agent (D), can enumerate: 2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate, Diethylene Glycol single-butyl ether acetic ester, ethylene glycol monobutyl ether, dipropylene glycol n-butyl ether, Diethylene Glycol dibutyl ether, dipropylene glycol list propyl ether etc.
Emulsifying agent (E)
In water-based metal surface treatment agent of the present invention, polymkeric substance (C) is scattered in the water by emulsifying agent (E), and said emulsifying agent was brought into use from the manufacturing stage of polymkeric substance (C).
As emulsifying agent (E), can only use reactive emulsifier (E1), can only use non-reacted emulsifying agent (E2), also can they combinations be used, consider from the viewpoint of the addition that can reduce emulsifying agent, preferably use reactive emulsifier.Under the situation of using reactive emulsifier, also become the constituent of polymkeric substance (C) from the polymer unit of reactive emulsifier (E1).
As reactive emulsifier (E1); Can enumerate: vinylsulfonate, styrene sulfonate, sulfo group ethyl-methyl acrylate, alkyl allyl group sulfosuccinate, thiazolinyl sulfosuccinate, polyoxyalkylene alkene ether vitriol, polyoxyalkylene alkene ether, polyxyethylated allyl phenyl ether, polyxyethylated allyl phenyl ether sulfuric acid, T 46155-1-(allyl group oxygen ylmethyl) alkyl ether sulphate salts, α-[1-{ (allyl group oxygen base) methyl }-2-(Nonylphenoxy) ethyl]-ω-hydroxyl T 46155, alpha-sulfo-ω-(1-(alkoxyl group) methyl-2-(2-propenyl oxygen base) oxyethyl group)-gather (Oxy-1,2-ethane two bases) salt etc.
As non-reacted emulsifying agent (E2), can enumerate: higher fatty acid salt (sodium laurate, sodium oleate etc.), higher alcohol sulfate salt (lauryl alcohol sodium sulfovinate, oleyl alcohol sodium sulfovinate etc.), senior alkyl arylsulphonate (X 2073, dodecyl diphenyl ether sodium disulfonate etc.), T 46155 nonylplenyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, polyethylene glycol mono-, YMS 2, polyglycol distearate etc.As above-mentioned salt, can enumerate sodium salt, sylvite, ammonium salt etc.
Then, use the usage rate of composition to describe to each.
The total mass M of the metal that composition (A) (zirconium compounds (A1) and/or metal oxide sol (A2)) is contained, need be 0.1～50 with the quality ratio [M/ (Si1+Si2)] of the quality Si2 of the contained silicon of the quality Si1 of the contained silicon of water-disintegrable silyl compound (B) and silicon-containing monomer (c2); Be preferably 1～20, more preferably 2～10.Above-mentioned quality ratio [M/ (Si1+Si2)] was less than 0.1 o'clock; Having because of blocking effect descends makes erosion resistance descend, solidify because of overlay film is remarkable the tendency that processibility is descended; Surpass at 50 o'clock, the tendency of adaptation decline, erosion resistance, alkali resistance and the acid resistance decline of film-forming properties decline, overlay film and base material or overlay film and face application layer is arranged.
The quality ratio Si1/Si2 of the quality Si2 of the silicon that the quality Si1 of the silicon that water-disintegrable silyl compound (B) is contained and silicon-containing monomer (c2) are contained need be 0.15～250, and is preferred 0.3～100, more preferably 0.5～50.Above-mentioned quality ratio Si1/Si2 had because of overlay film significantly solidifies the tendency that processibility is descended less than 0.15 o'clock, surpassed at 250 o'clock, and the tendency of the stability in storage that can not get this water-based metal surface treatment agent is arranged.
The combined amount of polymkeric substance (C) need be 40～98 quality %, preferred 50～98 quality %, more preferably 70～98 quality % with respect to all solids composition of water-based metal surface treatment agent of the present invention.When above-mentioned combined amount is less than 40 quality %, can not get good processibility and coating materials adaptation that polymkeric substance (C) is produced, when surpassing 98 quality %, can not get the mixed effect of composition (A) and water-disintegrable silyl compound (B).
The unitary ratio that respectively constitutes in the polymkeric substance (C) is stipulated as follows.From the unitary ratio of (methyl) propenoate (c1), be preferably 0.1～50 mass parts with respect to 100 mass parts polymkeric substance (C), more preferably 0.5～45 mass parts, further preferred 3～35 mass parts.When aforementioned proportion is lower than 0.1 mass parts; Be difficult to show the effect that this unit brings; The tendency that has erosion resistance, adaptation, didirtresistance, film-forming properties, ultraviolet resistance, alkali resistance, acid resistance and processibility to descend; When surpassing 50 mass parts, the overlay film tracing ability that adds man-hour descends, and the tendency that adaptation is bad, overlay film cracks is arranged.
From the unitary ratio of silicon-containing monomer (c2), be preferably 0.5～2.0 mass parts with respect to 100 mass parts polymkeric substance (C), more preferably 1.0～2.0 mass parts.When aforementioned proportion is lower than 0.5 mass parts, be difficult to show the effect that this unit brings, the tendency that has adaptation decline, erosion resistance, alkali resistance and acid resistance to descend when surpassing 2.0 mass parts, has overlay film to solidify and tendency that processibility is descended.
From α, the unitary ratio of β-ethylenically unsaturated carboxylic acids (c3) is stipulated with the acid number of polymkeric substance (C).The acid number of polymkeric substance (C) need be 5～40mgKOH/g, preferred 10～30mgKOH/g, more preferably 10～25mgKOH/g.Acid number is difficult to manifest the effect that this unit brings during less than 5mgKOH/g, has that not only adaptation descends but also the tendency of stability in storage variation, and when surpassing 40mgKOH/g, the water-soluble enhancing of the overlay film of formation has the tendency of alkali resistance and acid resistance decline.
The combined amount of softening agent (D) is confirmed according to the content of polymkeric substance (C) with as the value of the minimum film-forming temperature of the target of polymkeric substance (C).That is, confirm by the concrete formation of each polymkeric substance (C) with as the minimum film-forming temperature of target.In general, when the combined amount of softening agent (D) increased, minimum film-forming temperature reduced.
About the combined amount of emulsifying agent (E), the combined amount when only using reactive emulsifier (E1), with in the 100 mass parts polymkeric substance (C) from the shared proportional meter of the polymer unit of reactive emulsifier, be preferably 0.5～5 mass parts, more preferably 1～3 mass parts.When aforementioned proportion is lower than 0.5 mass parts, the tendency of the stability in storage that can not get water-based metal surface treatment agent of the present invention is arranged, when surpassing 5 mass parts, the water tolerance of the overlay film of formation descends, the tendency that has alkali resistance and acid resistance to descend.Combined amount when only using non-reacted emulsifying agent is preferably 3～10 mass parts with respect to 100 mass parts polymkeric substance (C), more preferably 5～8 mass parts.When above-mentioned combined amount is less than 3 mass parts, the tendency of the stability in storage that can not get water-based metal surface treatment agent of the present invention is arranged, when surpassing 10 mass parts, the tendency of the water tolerance decline of overlay film is arranged.Addition when reactive emulsifier and non-reacted emulsifying agent are used in combination can be regarded the addition that only adds when a kind of as and confirm.From the above, the whole addition of emulsifying agent is preferably 0.5～10 mass parts with respect to 100 mass parts polymkeric substance (C), more preferably 1～8 mass parts.
The not special restriction of the method for manufacture of polymkeric substance (C) can use existing known method to make polymkeric substance (C).For example, polymkeric substance (C) can use the polymeric method is carried out in polymerization starter, water, emulsifying agent (E) and the disposable mixing of monomer; The monomer dropping method; Methods such as preparatory emulsion process method are synthesized.Further, by seed polymerization, core-shell polymerization, polymerization of automatic feed for multistage polymerization of heterogeneous structure of particles (of the phase structure).Polymerization temperature is generally 0～100 ℃, and preferred 40～95 ℃, polymerization time is preferably 1～10 hour.
The not special restriction of polymerization starter for example can be used: ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide, Lucidol, peroxidized t-butyl perbenzoate, lauroyl peroxide, tertbutyl peroxide etc.
For emulsifying agent, as previously mentioned, use at least a portion under the situation of reactive emulsifier (E1), also become the integrant of polymkeric substance (C) from the polymerized unit of reactive emulsifier (E1).
This water-based metal surface treatment agent of the present invention in order to improve chemical-resistant and/or erosion resistance, can contain polymkeric substance (C) other resin that does not have unsaturated link(age) between carbon in addition in the scope of not damaging effect of the present invention.As this resin, can enumerate the vinyl resin that all do not have unsaturated link(age) between carbon, carbamate resins etc.As vinyl resin; Can enumerate gather (methyl) methyl acrylate, gather (methyl) Bing Xisuandingzhi, ROHM 2-ethylhexyl etc.; As carbamate resins; Can enumerate the polycondensate of polyvalent alcohols such as aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate and polyether glycol, polyester polyol.
The addition of other resin; Under the situation of vinyl resin; Total solids component 100 mass parts with respect to composition (A), water-disintegrable silyl compound (B) and polymkeric substance (C) are preferably below 70 mass parts, more preferably below 60 mass parts, further below preferred 50 mass parts.Under the situation of carbamate resins, be preferably below 90 mass parts with respect to 100 mass parts polymkeric substance (C), more preferably below 80 mass parts, further below preferred 70 mass parts.Surpass preferable range separately and when using, might can not get the erosion resistance, adaptation, didirtresistance, film-forming properties, ultraviolet resistance, alkali resistance, acid resistance and the processibility that produce by polymkeric substance (C).
This water-based metal surface treatment agent of the present invention; In the scope of not damaging effect of the present invention, can contain water-soluble solvent, rust-stabilising pigment, the tinting pigment that is useful on the flow agent that improves coating, is used to improve the drying property of overlay film, the additives such as wax that are used to improve oilness.As flow agent, can use anionic or cationic tensio-active agent, gathering of polyacetylene glycol be can enumerate and ethoxy alkane or polypropyleneoxide affixture, acetylenediol compound etc. encircled; As water-soluble solvent; Ethanol, Virahol, the trimethyl carbinol, Ucar 35 can be enumerated,, ETHYLE ACETATE, butylacetate can be enumerated as the ester class; As ketone, can enumerate acetone, methylethylketone, MIBK etc.
The method of manufacture of water-based metal surface treatment agent of the present invention is so long as can stably make the then not special restriction of the method for water-based metal surface treatment agent of the present invention.Treatment agent of the present invention; Generally can add the optional member of softening agent (D), composition (A) and water-disintegrable silyl compound (B) and use as required and make through in the dispersion liquid (emulsion or suspension-s) or solution of the polymkeric substance that obtains by above-mentioned polymerization (C).
The not special restriction of the solid component concentration of this water-based metal surface treatment agent of the present invention is preferably 3～50 quality %, more preferably 5～35 quality %.When being less than 3 quality %, coating possibly have problems, and the treatment agent cost up.When surpassing 50 quality %, the stability in storage of this water-based metal surface treatment agent has the tendency of decline.
Use the not special restriction of metallic substance of this water-based metal surface treatment agent of the present invention; For example can use: iron, with iron as the alloy of main body, aluminium, with aluminium as the alloy of main body, copper, be alloy of main body etc. with copper, also can use the metallization, the for example zinc-based metal plated steel sheet that on metallic substance arbitrarily, carry out plating.Water-based metal surface treatment agent of the present invention is best suited for zinc-based metal plated steel sheet.As zinc-based metal plated steel sheet; Can enumerate: steel plate galvanized, zinc-plated-the nickel steel plate, zinc-plated-the iron steel plate, zinc-plated-the chromium steel plate, zinc-plated-the aluminum steel plate, zinc-plated-titanium steel plate, zinc-plated-the magnesium steel plate, zinc-plated-manganese steel plate, zinc-plated-aluminium-the magnesium steel plate, zinc-plated-Al-Si-Mg steel plate etc.; Can also use the steel plate that in these coating, contains a small amount of cobalt, molybdenum, tungsten, nickel, titanium, chromium, aluminium, manganese, iron, magnesium, lead, bismuth, antimony, tin, copper, cadmium, arsenic etc. as dissimilar metal element or impurity, and the steel plate that in these coating, is dispersed with inorganicss such as silicon-dioxide, aluminum oxide, titanium oxide.In addition, water-based metal surface treatment agent of the present invention also can be applied to the multilayer coating with combinations such as the coating of above coating and other kind, for example iron plating, iron-phosphorus coating, nickel coatings, cobalt coating.The not special restriction of method for plating can be any one method in known plating method, calorizing, vapour deposition method, dispersion plating method, the vacuum-deposited coating etc.
This water-based metal surface treatment agent of the present invention can through be applied on the metallic substance and preferred 50～250 ℃, more preferably 70～150 ℃, further carry out drying under preferred 100～140 ℃ arrival temperature (temperature that metallic substance reaches) and be applied to metallic substance.When the arrival temperature was lower than 50 ℃, the solvent of this water-based metal surface treatment agent can not volatilize fully, and when being higher than 250 ℃, the part of the formed overlay film of this water-based metal surface treatment agent is decomposed.Dried compound film quality is preferably 0.05～5g/m 2, more preferably 0.2～3g/m 2, further preferred 0.5～2.5g/m 2Compound film quality is less than 0.05g/m 2The time, can not fully cover the surface of this metallic substance, thereby can not show each performance, more than 5g/m 2The time, adding and produce sediment man-hour, operability descends, thereby not preferred.
This water-based metal surface treatment agent is not limited to above-mentioned treatment process, also is applicable to the upper strata overlay film, the face application layer that carry out base treatment through phosphoric acid salt etc., and the silane coupling agent that therefore also can be used as pre-coated steel plate uses.
Embodiment
Below, enumerate embodiments of the invention and comparative example the present invention is described particularly, but the invention is not restricted to these examples.Preparation, embodiment and the comparative example of test board and the coating process of water-based metal surface treatment agent are described.
[making of metal finishing steel plate]
(1) constituent of water-based metal surface treatment agent
Table 1 expression employed zirconium compounds (A1).
Table 2 expression employed metal oxide sol (A2).
Table 3 expression employed water-disintegrable silyl compound (B).
The monomer of the table 4 employed formation polymkeric substance of expression (C).
Table 5 expression employed softening agent (D).
Table 6 expression the emulsifying agent that uses (E).
(2) manufacturing of polymkeric substance (C) dispersion liquid example
With the inner air of the four-hole boiling flask that whisking appliance, reflux exchanger, tap funnel and TM are installed with nitrogen replacement after, add 120 mass parts ion exchanged waters and 1.5 mass parts エ レ ミ ノ, one Le JS-2.In tap funnel, add isobornyl methacrylate 35 mass parts, TEB 3K 20 mass parts, 2-EHA 20 mass parts, n-BMA 20 mass parts, vinyl three (methoxy ethoxy) silane 1 mass parts and vinylformic acid 5 mass parts and mixing, obtain mix monomer.Then, flask is warming up to 70 ℃ after, in flask, add the mix monomer of 10 quality %, add ammonium persulphate 0.3 mass parts then.After reaction finishes, with the mix monomer that dripped remaining 90 quality % in 3 hours.To make the flask temperature after drip finishing be 75 ℃ and kept 1 hour.After being cooled to 40 ℃, using ammoniacal liquor is 7 with pH regulator, adds Diethylene Glycol single-butyl ether acetic ester 30 mass parts, processes surface treatment liquid.This dispersion liquid is equivalent to polymkeric substance (C) dispersion liquid (reference table 7) of C4.
Other polymkeric substance (C) or the dispersion liquid that is not equivalent to the polymkeric substance of polymkeric substance (C) are also made (reference table 7) according to same program.Polymkeric substance (C) or not to be equivalent to the composition and the second-order transition temperature of polymkeric substance of polymkeric substance (C) as shown in table 7.
(3) preparation method of the water-based metal surface treatment agent of embodiment 1～63 and comparative example 1～19
At room temperature; In zero(ppm) water, add the dispersion liquid (C1～C26) or be not equivalent to the dispersion liquid (C27～C36) of the polymkeric substance of polymkeric substance (C) of zirconium compounds (A1), metal oxide sol (A2), water-disintegrable silyl compound (B) and polymkeric substance (C) with the ratio shown in table 8～11; Mix the water-based metal surface treatment agent shown in preparation table 8～11 with whisking appliance.In addition, the solid component concentration of water-based metal surface treatment agent is 30 quality %.
(4) preparation method of the water-based metal surface treatment agent of embodiment 64
In the water-based metal surface treatment agent of the embodiment 57 of table 10,10 quality % in the solids component ratio of polymkeric substance (C) are partly become polyester polyol type carbamate resins.Polyester polyol type carbamate resins is through will be by 1 with triethylamine; Polyester polyol 170 mass parts, 1 that 4-butyleneglycol and hexanodioic acid obtain; Hexamethylene-diisocyanate 30 mass parts, 2, the reaction of 2-dimethylol propionic acid 25 mass parts and N-N-methyl-2-2-pyrrolidone N-100 mass parts and the prepolymer that obtains are dispersed in the deionized water and obtain, second-order transition temperature is that 100 ℃ and minimum film-forming temperature are the aqueous urethane resin below 0 ℃.
Comparative example 20
According to the ratio of components of the embodiment shown in the table 9 57,1.0 quality % in the solids component ratio of polymkeric substance (C) are partly become resol (Showa Highpolymer Co., Ltd's system with the solids component proportional meter; シ ヨ one ノ one Le BRL-157).
Comparative example 21
Use the embodiment 6 of record in the patent documentation 1 (TOHKEMY 2000-327704 communique), under the treatment condition of table 11 record, form overlay film, and be used for estimating.
Comparative example 22
Use the embodiment 5 of record in the patent documentation 2 (TOHKEMY 2000-327722 communique), under the treatment condition of table 11 record, form overlay film, and be used for estimating.
Comparative example 23
Use the embodiment 9 of record in the patent documentation 4 (TOHKEMY 2003-201579 communique), under the treatment condition of table 11 record, form overlay film, and be used for estimating.
Comparative example 24
Use the embodiment 1 of record in the patent documentation 5 (TOHKEMY 2006-52348 communique), under the treatment condition of table 11 record, form overlay film, and be used for estimating.
Comparative example 25
Use the embodiment 2 of record in the patent documentation 6 (TOHKEMY 2006-152056 communique), under the treatment condition of table 11 record, form overlay film, and be used for estimating.
(4) metallic substance
Commercially available metallic substance shown in below using.
Pot galvanize-55% duraluminum steel plate (GL): thickness of slab=0.8mm, plating amount=150/150 (g/m 2)
(5) skimming treatment
(registered trademark: Nihon Parkerizing Co., Ltd.'s system) concentration with 20g/L is dissolved in the water with silicates alkaline defatting agent Off ア イ Application Network リ one Na 1; With the degreasing fluid that obtains material is carried out spraying in 2 minutes under the condition of 60 ℃ of temperature and handle, carry out drying after cleaning for 30 seconds with pure water.The disposable plates of using gained is as test board.
(6) making of surface treated steel plate
With on the test board surface of wound rod coating machine separate application after the skimming treatment, drying obtains surface treated steel plate under 280 ℃ environment with each treatment agent of embodiment 1～47 and comparative example 1～21.In addition, reach plate temperature (PMT), carry out the adjusting of compound film quality through the solid component concentration of regulating the water-based metal surface treatment agent through regulating to be up to time of drying.PMT and compound film quality are as shown in table 11.
[evaluation method]
(1) erosion resistance
According to JASO M609; Carrying out with brine spray (35 ± 2 ℃ following 2 hours), dry (60 ± 1 ℃ following 4 hours), wetting (50 ± 1 ℃ following 2 hours) is 1 round-robin compound cycle test, confirms the white rust production of 144 undressed portions of circulation time, cross cutting part, end face portion.
< metewand >
Undressed portion: the generation area of the white rust that day test and appraisal valency is undressed.
◎: no white rust produces
Zero: it is below 10% of the total area that white rust produces area occupation ratio
△: white rust produce area occupation ratio surpass the total area 10% and be below 30%
*: white rust produce area occupation ratio surpass the total area 30% and be below 50%
* *: white rust produces area occupation ratio and surpasses 50% of the total area
Cross cutting part: on the surface of surface treated steel plate, carry out the cross cutting with cutter, measure from the width of the white rust of cross cutting part generation.
◎: the white rust width is below the 2mm
Zero: the white rust width surpasses 2mm and is below the 5mm
△: the white rust width surpasses 5mm and is below the 8mm
*: the white rust width surpasses 8mm and is below the 12mm
* *: white rust width surpasses 12mm
End face portion: the end of surface treated steel plate is cut away, measure the width of the white rust that produces from the part of exposing metallic substance.
◎: the white rust width is below the 5mm
Zero: the white rust width surpasses 5mm and is below the 10mm
△: the white rust width surpasses 10mm and is below the 15mm
*: the white rust width surpasses 15mm
(2) face application layer adaptation
Use the wound rod coating machine, coating melamine phthalic resin coating on surface treated steel plate, making its dry film thickness is 25 μ m, under 130 ℃ furnace temperature, bakes 20 minutes.Then, mark 1mm, 100 checker, again Erichsen cupping (Erichsen) processing is carried out with the overflow mould of 7mm in this position with cutter.Part to after the enforcement processing is carried out belt stripping test, the residual number of evaluating resin layer.
< metewand >
◎: 100
More than zero: 98 and be less than 100
△: more than 50 and be less than 98
*: be less than 50
(3) base material adaptation
Overflow mould with 7mm carries out the processing of Erichsen cupping to surface treated steel plate, and implements the belt stripping test of processing portion.Visual assessment is peeled off state.
< metewand >
◎: do not have and peel off
Zero: peel off area and surpass 1% and be below 20%
△: peel off area and surpass 20% and be below 50%
*: peel off area and surpass 50%
(4) didirtresistance
, wash after the winding-up to the jet black face material dispersion liquid of 10 quality % of surface treated steel plate with atomizer, estimate through the tonal variation (Δ E) before and after the test.Tonal variation is used Color Meter ZE2000 (NIPPON DENSHOKU system, light source: halogen lamp 12V/2A) measure.Following ultraviolet resistance, alkali resistance, acid proof tonal variation also are same.
< metewand >
◎：ΔE≤1
○：1＜ΔE≤3
△：3＜ΔE≤5
×：5＜ΔE
(5) film-forming properties
Condition of surface through observe surface treated steel plate with AFM (AFM) is estimated.
< determinating reference >
◎: observe uniform overlay film
Zero: observe concavo-convex few uniform overlay film
△: observe irregular overlay film
*: observe the overlay film that can confirm the particle of polymkeric substance clearly
(6) ultraviolet resistance
With the ultraviolet ray of fluorescence ultraviolet ray dampening unit (the wetting exposure test machine of UVCON luminescent lamp ultraviolet ray) to 4 hours 365nm of surface treated steel plate irradiation; Under 50 ℃ of envrionment temperatures, humidity 60%Rh, left standstill 2 hours then; Above-mentioned condition is made as 1 circulation; Implement 196 circulations, the tonal variation (Δ E) before and after the evaluation test.
< metewand >
◎：ΔE≤1
○：1＜ΔE≤3
△：3＜ΔE≤5
×：5＜ΔE
(7) alkali resistance
Surface treated steel plate was flooded 10 minutes the tonal variation (Δ E) before and after the evaluation test in 25 ℃ 3 quality % aqueous sodium hydroxide solutions.
< metewand >
◎：ΔE≤1
○：1＜ΔE≤3
△：3＜ΔE≤5
×：5＜ΔE≤10
××：10＜ΔE
(8) acid resistance
Surface treated steel plate was flooded 3 hours the tonal variation (Δ E) before and after the evaluation test in 25 ℃ 3 quality % sulfuric acid.
< metewand >
◎：ΔE≤1
○：1＜ΔE≤3
△：3＜ΔE≤5
×：5＜ΔE≤10
××：10＜ΔE
(9) processibility
Faulted condition through utilizing universal testing machine to carry out bead (draw bead) test back observation surface treated steel plate surface is estimated.Drawing condition is compacting 0.5 ton of load, muscle tip radii 5mm, drawing speed 5cm/ second.
◎: not damaged
Zero: damage is arranged slightly
△: there is burn the part
*: integral body has burn
(10) stability in storage
The water-based metal surface treatment agent is left standstill in 40 ℃ environment, estimate stability in storage with the time till gelation.
◎: more than 6 months
More than zero: 3 month and be less than 6 months
△: more than 1 month and be less than 3 months
*: be less than 1 month
Evaluation result is shown in table 13～16.Can know by table 13～15, use under the situation of water-based metal surface treatment agent of the present invention, can access the surface treated steel plate of erosion resistance, adaptation, didirtresistance, film-forming properties, ultraviolet resistance, alkali resistance, acid resistance and excellent processability.In addition, can know the having excellent storage stability of water-based metal surface treatment agent of the present invention by table 13～15.
Relative therewith, use (methyl) propenoate (c1) comparative example 1, do not use the comparative example 2 of silicon-containing monomer (c2), various erosion resistances and poor, and alkali resistance, acid resistance are poor with the adaptation of application layer and base material.Acid number is greater than the comparative example 5 of specialized range, and the water tolerance of overlay film descends, thereby the remarkable variation of various erosion resistance, and alkali resistance, acid resistance are also poor for the same reason.On the contrary, acid number is less than the comparative example 4 of specialized range, and various erosion resistances are poor slightly, the remarkable variation of stability in storage.Minimum film-forming temperature is lower than the comparative example 6 of specialized range; It is comparatively good to have sufficient film-forming properties thereby performance, but because softening agent remains in the overlay film, thereby alkali resistance, acid resistance are poor; On the contrary; Minimum film-forming temperature is higher than the comparative example 7 of specialized range, and film forming is incomplete, thereby various erosion resistance, application layer and base material adaptation, alkali resistance, acid resistance are poor.Second-order transition temperature is lower than the comparative example 8 of specialized range, and alkali resistance, acid resistance are poor, and second-order transition temperature is higher than the comparative example 9 of specialized range, and overlay film is really up to the mark thereby the base material adaptation is poor.Polymkeric substance (C) contains cinnamic comparative example 17 and 18, the remarkable variation of ultraviolet resistance.In addition, contain the comparative example 19 of vinylformic acid diamantane ester in the polymkeric substance (C), because of vinylformic acid diamantane ester causes film-forming properties bad, thereby various erosion resistance, application layer and base material adaptation, alkali resistance, acid resistance, poor storage stability.Use the comparative example 20～25 of the water-based metal surface treatment agent of putting down in writing in the patent documentation described in the background technology, erosion resistance, ultraviolet resistance and alkali-proof at least a character are poor.
Then, M/ (Si1+Si2) and Si1/Si2 are described.At first; Make Si1/Si2 basic maintenance necessarily and the embodiment 27 to 36 that M/ (Si1+Si2) is changed in specialized range in specialized range; The comparative example 10 that is lower than specialized range with M/ (Si1+Si2) is compared; The adaptation of application layer and base material is good, and the comparative example 11 that surpasses specialized range with M/ (Si1+Si2) is compared, and various erosion resistances, processibility, has excellent storage stability.In addition; Si1/Si2 is in optimum range and the also embodiment in optimum range 31,32 of M/ (Si1+Si2); The embodiment 27 to 30 that is lower than optimum range with M/ (Si1+Si2) compares, particularly various erosion resistances, ultraviolet resistance, alkali resistance, acid resistance, excellent processability, on the contrary; The embodiment 33 to 36 that surpasses optimum range with M/ (Si1+Si2) compares particularly various erosion resistances, application layer and base material adaptation, ultraviolet resistance, excellent processability.Composition (A) is replaced with by zirconium compounds (A1) among the embodiment 37 to 46 of metal oxide sol (A2) and also have same tendency.
On the other hand; Make M/ (Si1+Si2) basic maintenance necessarily and the embodiment 47 to 55 that Si1/Si2 is changed in specialized range in specialized range; The comparative example 14 that is lower than specialized range with Si1/Si2 is compared; Various erosion resistances, base material adaptation, film-forming properties, alkali resistance, acid-proof, the comparative example 15 that surpasses specialized range with Si1/Si2 is compared various erosion resistances, application layer and base material adaptation, ultraviolet resistance, alkali resistance, acid-proof.In addition; M/ (Si1+Si2) keeps certain in specialized range basically and Si1/Si2 is the embodiment 50 to 53 of optimum range; The embodiment 47 to 49 that is lower than optimum range with Si1/Si2 compares, and cutting part erosion resistance, acid resistance, tendency that adding property is good is arranged, on the contrary; The embodiment 54,55 and the comparative example 16 that surpass optimum range with Si1/Si2 are compared, and processibility, have excellent storage stability.
Hence one can see that; When any one among M/ of the present invention (Si1+Si2) and the Si1/Si2 departs from the scope of regulation; At least two kinds in erosion resistance, application layer and base material adaptation, didirtresistance, film-forming properties, ultraviolet resistance, alkali resistance, acid resistance, processibility, stability in storage can not get sufficient performance in nature; On the contrary, when both were optimum range, above-mentioned all character all can access very good performance.
Table 1
Table 2
Figure BPA00001294055900272
Table 3
Figure BPA00001294055900273
Table 4
Figure BPA00001294055900281
Table 5
Figure BPA00001294055900282
Table 6
Figure BPA00001294055900283
Figure BPA00001294055900291
Figure BPA00001294055900301
Figure BPA00001294055900321
Figure BPA00001294055900331
Table 12
Figure BPA00001294055900341
The unit of adhesion amount and PMT is respectively g/m 2With ℃.
Figure BPA00001294055900351
Figure BPA00001294055900371
Figure BPA00001294055900381

Claims (10)

1. water-based metal surface treatment agent; Contain composition A, water-disintegrable silyl compound B, polymkeric substance C, softening agent D and emulsifying agent E; Said composition A is selected from least a in the group of being made up of zirconium compounds A1 and metal oxide sol A2; The polymerized unit of the silicon-containing monomer c2 that said polymkeric substance C has the polymerized unit of (methyl) propenoate c1 that representes from following general formula I, represent from following general formula I II, from α; The polymerized unit of β-ethylenically unsaturated carboxylic acids c3 and from the polymerized unit of other (methyl) propenoate c4 as polymerized unit, and do not contain the unsaturated link(age) beyond the carbonyl in the molecule, the second-order transition temperature of this polymkeric substance C be 0～70 ℃, minimum film-forming temperature for-5～40 ℃, acid number be 5～40mgKOH/g; Wherein
Emulsifying agent E is selected from least a in the group of being made up of reactive emulsifier E1 and non-reacted emulsifying agent E2; In at least a portion is under the situation of reactive emulsifier; This reactive emulsifier with from the form of the polymerized unit of this reactive emulsifier as a kind of of the polymerized unit of polymkeric substance C and exist; Polymkeric substance C is disperseed by emulsifying agent E; The total mass M of the metal that composition A is contained, with the quality ratio [M/ (Si1+Si2)] of the total quality of the quality Si2 of the contained silicon of the quality Si1 of the contained silicon of water-disintegrable silyl compound B and silicon-containing monomer c2 be 0.1～50; And Si1/Si2 is 0.15～250, and the ratio of polymkeric substance C is 40～98 quality % with respect to all solids composition of this water-based metal surface treatment agent
Figure FSB00000904644900011
Among the formula I, R1 representes Wasserstoffatoms or methyl, and R2 representes the group shown in the general formula I I,
Figure FSB00000904644900012
Among the formula II, R3, R4 and R5 represent the alkyl of Wasserstoffatoms, hydroxyl or carbonatoms 1～3 independently of each other,
Figure FSB00000904644900021
In the formula III, R6, R7 and R8 represent the alkyl of Wasserstoffatoms, hydroxyl, carbonatoms 1～3 or the alkoxyl group of carbonatoms 1～3 independently of each other, the group shown in X expression IV or the general formula V,
Figure FSB00000904644900022
Among the formula V, R9 representes Wasserstoffatoms or methyl, and R10 representes the alkylidene group of carbonatoms 1～12.
2. treatment agent as claimed in claim 1, wherein, softening agent D is for being selected from by 2,2,4-trimethylammonium-1, at least a in the group that 3-pentanediol mono isobutyrate, Diethylene Glycol single-butyl ether acetic ester, ethylene glycol monobutyl ether and dipropylene glycol n-butyl ether are formed.
3. treatment agent as claimed in claim 1 wherein, is 0.1～50 mass parts from the unitary ratio of (methyl) propenoate c1 with respect to 100 mass parts polymkeric substance C.
4. treatment agent as claimed in claim 2 wherein, is 0.1～50 mass parts from the unitary ratio of (methyl) propenoate c1 with respect to 100 mass parts polymkeric substance C.
5. treatment agent as claimed in claim 1, wherein, metal oxide sol A2 is selected from least a in the group of being made up of cerium oxide sol, yttrium oxide colloidal sol, Neodymium trioxide colloidal sol and lanthanum trioxide colloidal sol.
6. treatment agent as claimed in claim 2, wherein, metal oxide sol A2 is selected from least a in the group of being made up of cerium oxide sol, yttrium oxide colloidal sol, Neodymium trioxide colloidal sol and lanthanum trioxide colloidal sol.
7. treatment agent as claimed in claim 3, wherein, metal oxide sol A2 is selected from least a in the group of being made up of cerium oxide sol, yttrium oxide colloidal sol, Neodymium trioxide colloidal sol and lanthanum trioxide colloidal sol.
8. treatment agent as claimed in claim 4, wherein, metal oxide sol A2 is selected from least a in the group of being made up of cerium oxide sol, yttrium oxide colloidal sol, Neodymium trioxide colloidal sol and lanthanum trioxide colloidal sol.
9. like each described treatment agent in the claim 1～8, wherein, the ratio of emulsifying agent E is 0.5～5 mass parts with respect to 100 mass parts polymkeric substance C.
10. metallic substance, its surface has 0.05～5g/m 2The dry overlay film that forms by each described water-based metal surface treatment agent in the claim 1～9.
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CN116875093B (en) * 2023-07-13 2024-05-07 山东辉石能源工程有限公司 Liquid sol steel anti-corrosion coating and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002275648A (en) * 2001-03-15 2002-09-25 Nippon Paint Co Ltd Metal surface treating agent
JP2004131549A (en) * 2002-10-09 2004-04-30 Shin Etsu Chem Co Ltd Primer composition, method for coating the composition, and coated article

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4435950A1 (en) * 1994-10-07 1996-04-11 Hoechst Ag Copolymers with cyclic or polycyclic monomers with a special isomer distribution and their use in coating compositions
KR100989539B1 (en) * 2005-12-15 2010-10-25 니혼 파커라이징 가부시키가이샤 Surface treatment for metal materials, surface treatment process, and surface- treated metal materials

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002275648A (en) * 2001-03-15 2002-09-25 Nippon Paint Co Ltd Metal surface treating agent
JP2004131549A (en) * 2002-10-09 2004-04-30 Shin Etsu Chem Co Ltd Primer composition, method for coating the composition, and coated article

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